Hydrofining catalysts

ABSTRACT

A catalyst composition is prepared by dissolving a suitable vanadium and oxygen containing compound, a suitable nickel (II) compound and ammonia in water, mixing this solution with an alumina containing support material, and calcining this mixture. This catalyst composition is used primarily for hydrotreating of hydrocarbon feed stream, which contain nickel, vanadium and sulfur impurities, particularly heavy oils.

BACKGROUND OF THE INVENTION

In one aspect, this invention relates to a process for preparing apromoted, alumina-based catalyst composition. In another aspect, thisinvention relates to catalytic hydrotreating of liquid hydrocarboncontaining feed streams, in particular heavy oils.

The use of alumina, promoted with transition metals or compoundsthereof, for hydrotreating (e.g., demetallizing, desulfurizing,hydrocracking) liquid hydrocarbon feed streams, which contain cokeprecursors and metal, sulfur, and nitrogen impurities, such as heavypetroleum oils and fractions thereof is well known. However, there is anever present need to develop new methods of preparing such catalysts andto develop new catalysts that are more effective in removing undesirableimpurities from such feed streams.

SUMMARY OF THE INVENTION

It is an object of this invention to provide an effective hydrofiningcatalyst composition. It is another object of this invention to providea process for preparing a new catalyst composition. It is still anotherobject of this invention to provide a new impregnating solution, to beused primarily for preparing catalyst compositions. It is a furtherobject of this invention to employ a new and effective catalyst for theremoval of impurities from heavy hydrocarbon containing oils. Otherobjects and advantages will be apparent from the detailed descriptionand the appended claims.

In accordance with this invention, a composition of matter (suitable asa catalyst composition) containing vanadium, nickel and alumina isprepared by a process comprising the steps of:

(A) mixing (a) at least one vanadium and oxygen containing compound (b),at least one nickel(II) compound, (c) ammonia and (d) water, in suchamounts and under such conditions as to obtain a solution;

(B) mixing said solution obtained in step (A) with an alumina-containingsupport material;

(C) heating the mixture obtained in step (B) at a first temperatureunder such conditions as to at least partially dry said mixture; and

(D) heating (calcining) the at least partially dried mixture obtained instep (C) at a second temperature, which is higher than said firsttemperature, under such conditions as to activate said mixture.

In one embodiment, the process of this invention comprises apresulfiding step (F) after step (D).

In another embodiment of this invention, an aqueous solution as preparedby step (A) is provided. This solution is preferably used forimpregnating substantially inert support materials so as to preparecatalyst compositions.

In still another embodiment of this invention, the catalyst compositionprepared by the process of this invention comprising steps (A), (B), (C)and (D) is used for contacting with a free hydrogen containing gas and ahydrocarbon containing feed stream, which also contains compounds ofsulfur, nickel and vanadium, under such conditions as to produce ahydrocarbon containing stream having reduced levels of sulfur, nickeland vanadium.

DETAILED DESCRIPTION OF THE INVENTION

Preferably the vanadium compound and oxygen containing compound (a) usedin step (A) of the process of this invention is selected from the groupconsisting of ammonium and alkali metal orthovanadates, ammonium andalkali metal pyrovanadates, ammonium and alkali metal metavanadates,divanadium pentoxide and hydrated forms thereof, vanadium dioxide andhydrated forms thereof, divanadium trioxide and hydrated forms thereof.

Preferably the nickel (II) compound (i.e., divalent nickel compound) (b)used in step (B) of the process of this invention is selected from thegroup consisting of nickel carbonate, nickel bicarbonate, basic nickelcarbonate (Ni₂ (OH)₂ (CO₃)), nickel nitrate, nickel sulfate, nickelhalides, nickel acetate, nickel formate, nickel oxalate, nickelcarboxylates containing from 3-12 carbon atoms, nickel oxide and nickelhydroxide.

It is presently preferred to carry out step (A) under such conditionsand using such amounts of (a), (b), (c) and (d) as to obtain asubstantially clear solution. It is believed that this solutioncomprises complex cations that contains divalent nickel (i.e., Ni⁺²) andammonia, and anions that contain vanadium and oxygen. However, it iswithin the scope of this invention to obtain in step (A) a solutionhaving solid particles dispersed therein. In this case, the solutionplus dispersed solids can be used as is in step (B), or preferably, thedispersed solid particles are separated from the solution by anysuitable separation means such as filtration, centrifugation or settlingand subsequent draining before step (B).

In a presently most preferred embodiment, the vanadium compound is NH₄VO₃, the nickel compound is NiCO₃, and ammonia is added as aconcentrated aqueous solution containing about 5-10 mole/1 NH₃. Thesolution obtained in step (A) preferably contains the followingconcentrations of V and Ni, given as the number of gram-atomic weights(herein referred to as mole) per liter solution, and of NH₃, given asthe number of gram-molecular weights (herein also referred to as mole)per liter solution:

    ______________________________________                                                  Broad    Intermediate                                                                             Narrow                                          ______________________________________                                        Mole/l of V 0.005-4.0  0.01-1.5   0.03-0.5                                    Mole/l of Ni                                                                              0.005-4.0  0.01-1.5   0.03-0.5                                    Mole/l of NH.sub.3                                                                         0.03-10   0.1-6      0.3-2                                       ______________________________________                                    

In one embodiment of this invention, the solution obtained in step (A)is provided and used as is for purposes other than makingalumina-supported catalysts. For instance, the solution can be used forimpregnating substantially inert support materials such as silica,alumino-silicates (e.g., zeolites), titania, metal phosphates and thelike, so as to make a variety of catalysts, preferably for hydrogenationand hydrocracking reactions. However, it is within the scope of thisinvention to use this solution for purposes other than catalystpreparation. Solid particles dispersed in the solution can be removed bythe above-described separation means.

The alumina-containing support material employed in step (B) can besubstantially pure alumina or partially hydrated forms thereof.Preferably the alumina-containing support material is a finely dividedsolid. Generally the surface area (determined by BET/N₂ ; ASTM D3037) ofthe alumina-containing material ranges from about 20 m² /g to about 350m² /g. The support material may contain transition metals (e.g., Mo, Ni)or compounds thereof, usually at a level of less than 1 weight-% metals,based on the weight of the entire alumina-containing support material(before impregnation step (A)). It is within the scope of this inventionto employ mixtures of alumina and other inorganic refractory materialssuch as silica, silica-alumina, alumino-silicates, magnesia, titania,zirconia, aluminum phosphate, zirconium phosphate and the like. If aphosphate is present, the amount is generally less than 10 weight-% P,based on the weight of the alumina-containing support material (beforeimpregnation).

The drying step (C) is generally carried out in air or an inert gas, ata temperature ranging from about 25° C. to about 200° C. (preferably50°-100° C.) so as to remove the greatest portion of water from themixture obtained in step (B). Vacuum conditions may be employed but arepresently not preferred. The at least partially dried mixture generallycontains less that about 20 weight-% water. The rate of drying iscontrolled so as to avoid surges of water vapor that can cause theimpregnating solution to splatter and to excessively accumulate incertain surface regions of the solid support material. Depending on thedrying temperature and specific drying conditions (such as extent of airmovement, thickness of the solid layer to be dried), the drying timeranges generally from about 0.5 hour to about 100 hours, preferably fromabout 1 hour to about 30 hours.

It is presently believed that the activation occurring in calcining step(D) is the result of an at least partial conversion of the nickel andvanadium compounds of step (A) to oxidic compounds of Ni and V. Theterms "activate" and "activation" as used herein mean that the calcinedcatalyst composition of this invention is a more effective catalyst forhydrotreating reactions, particularly hydrodemetallization andhydrodesulfurization of liquid hydrocarbon containing feed streams, thanthe at least partially dried mixture obtained in step (C). Preferredheating calcining conditions in step (D) comprise heating (generally ina non-reducing gas atmosphere) a temperature ranging from about 200° C.to about 600° C. (more preferably 300°-600° C.), and a heating timeranging from 0.5 to about 10 hours. A presently more preferred specificcalcining program is described in Example I. Generally the heating iscarried out in a free oxygen containing gas, preferably air. But othergases, e.g., hydrogen, nitrogen, helium, neon, argon, krypton, xenon,hydrogen sulfide or mixtures thereof may also be employed.

The thus calcined catalyst composition of this invention generallycomprises from about 0.1 to about 5.0, preferably from about 0.5 toabout 2.0, weight-% V, based on the weight of the entire catalystcomposition; and from about 0.1 to about 5.0, preferably from about 0.5to about 2.0, weight-% Ni, based on the weight of the entire catalystcomposition. The surface area (determined by the BET/N₂ method; ASTMD3037) of the calcined catalyst composition of this invention rangesfrom about 20 to about 350 m² /g, preferably from about 100 to about 250m² /g. The catalyst composition can be pelletized or compacted intovarious shapes (e.g., spherical cylindrical or trilobal) for convenientshipping and use in fixed catalyst beds.

In one embodiment, the calcined catalyst composition of this inventionis presulfided by the additional step (F) of contacting the calcinedcatalyst composition with a suitable sulfur compound under suchconditions as to at least partially convert the transition metalcompounds contained in the calcined catalyst composition to sulfides.This can be accomplished by passing a sulfur-containing gas oil or asolution of COS or mercaptans or organic sulfides, e.g., in ahydrocarbon solvent, over the catalyst composition at an elevatedtemperature (e.g., at 300°-650° F.), generally in the presence ofhydrogen gas. Or a gaseous mixture of hydrogen and hydrogen sulfide(e.g. at a volume ratio of about 10:1) can be passed over the catalystcomposition at an elevated temperature, preferably 1-15 hours at about400° F. and then 1-15 hours at about 700° F. This presulfiding step isparticularly desirable when the catalyst composition of this inventionis used for hydrotreating or hydrocracking of liquid hydrocarboncontaining feed streams.

The composition of matter of this invention can be used as a catalystcomposition for a variety of reactions such as hydrocarbon conversionreactions. In one preferred embodiment of this invention, the catalystcomposition of this invention is used as a catalyst for hydrotreatingsubstantially liquid hydrocarbon containing feed streams, which alsocontain compounds of sulfur, nickel and vanadium as impurities, andgenerally also asphaltenes, coke precursors (measured as Ramsbottomcarbon residue) and nitrogen compounds. Suitable hydrocarbon containingfeed streams include crude oil and fractions thereof, petroleumproducts, heavy oil extracts, coal pyrolyzates, liquefied coal products,products from tar sands, shale oil and shale oil products. The catalystcomposition of this invention is particularly suited for treating heavytopped crudes and heavy oil residua, which generally have an initialboiling point in excess of about 400° F., preferably in excess of about600° F., containing about 10-1000 ppmw (parts per million by weight) ofvanadium, about 5-500 ppmw of nickel, about 0.5-5 weight-% of sulfur,about 0.2-2 weight-% of nitrogen, and having an API⁶⁰ gravity of about5-25.

The hydrotreating process employing the catalyst composition of thisinvention is carried out in any suitable apparatus whereby an intimatecontact of the catalyst composition with said hydrocarbon containingfeed stream and a free hydrogen containing gas is achieved, under suchconditions as to produce a hydrocarbon containing stream having reducedlevels of nickel, vanadium and sulfur. Generally, lower levels ofnitrogen and Ramsbottom carbon residue and a higher value of API⁶⁰gravity are also attained in this hydrotreating process. Thehydrotreating process can be carried out using a fixed catalyst bed(presently preferred) or a fluidized catalyst bed or a moving catalystbed or an agitated slurry of the catalyst in the oil feed(hydrovisbreaking operation). The hydrocarbon hydrotreating process canbe carried out as a batch process or, preferably, as a continuousprocess.

The catalyst composition of this invention can be used in saidhydrotreating process alone in a reactor or can be used in combinationwith essentially inert materials such as alumina, silica, titania,magnesia, silicates, metal aluminates, alumino-silicates (e.g.,zeolites), titania and metal phosphates. Alternating layers of the inertmaterial and of the catalyst composition can be used, or the catalystcomposition can be mixed with the inert material. Use of the inertmaterial with the catalyst composition provides for better dispersion ofthe hydrocarbon containing feed stream. Also, other catalysts such asknown hydrogenation and desulfurization catalysts (e.g., NiO/MoO₃,CoO/MoO₃ or NiO/CoO/MoO₃ on alumina) may be used with the catalystcomposition of this invention to achieve simultaneous demetallization,desulfurization, denitrogenation, hydrogenation and hydrocracking, ifdesired. In one embodiment of said hydrocarbon hydrotreating process,the catalyst composition of this invention has been presulfided asdescribed above before being used.

Any suitable reaction time between the catalyst composition and thehydrocarbon containing feed stream and hydrogen gas can be utilized. Ingeneral, the reaction time will range from about 0.05 hours to about 10hours. Preferably, the reaction time will range from about 0.4 to about5 hours. Thus, the flow rate of the hydrocarbon containing feed streamshould be such that the time required for the passage of the mixturethrough the reactor (residence time) will preferably be in the range ofabout 0.4 to about 5 hours. In a continuous fixed bed operation, thisgenerally requires a liquid hourly space velocity (LHSV) in the range ofabout 0.10 to about 20 cc of feed per cc of catalyst per hour,preferably from about 0.2 to about 2.5 cc/cc/hr.

The hydrotreating process employing the catalyst composition of thepresent invention can be carried out at any suitable temperature. Thereaction temperature will generally be in the range of about 250° C. toabout 550° C. and will preferably be in the range of about 350° C. toabout 450° C. Higher temperatures do improve the removal of metals, buttemperatures which will have adverse effects on the hydrocarboncontaining feed stream, such as excessive coking, will usually beavoided. Also, economic considerations will usually be taken intoaccount in selecting the operating temperature. Lower temperatures cangenerally be used for lighter feeds.

Any suitable pressure may be utilized in the hydrotreating process. Thereaction pressure will generally be in the range of about atmosphericpressure (0 psig) to up to about 5,000 psig. Preferably, the pressurewill be in the range of about 100 to about 2500 psig. Higher pressurestend to reduce coke formation but operating at high pressure may beundesirable for safety and economic reasons.

Any suitable quantity of hydrogen gas can be added to the hydrotreatingprocess. The quantity of hydrogen gas used to contact the hydrocarboncontaining feed stock will generally be in the range of about 100 toabout 10,000 standard cubic feet H₂ per barrel of the hydrocarboncontaining feed stream and will more preferably be in the range of about1000 to about 6000 standard cubic feet H₂ per barrel of the hydrocarboncontaining feed stream.

In general, the catalyst composition is utilized primarily fordemetallization until a satisfactory level of metals removal is nolonger achieved which generally results from the coating of the catalystcomposition with coke and metals being removed from the feed. It ispossible to remove the metals from the catalyst composition. But theseprocedures are expensive, and it is generally contemplated that once theremoval of metals falls below a desired level, the spent (deactivated)catalyst will simply be replaced by a fresh catalyst.

The time in which the catalyst composition of this invention willmaintain its activity for removal of metals and sulfur will depend uponthe metals concentration in the hydrocarbon containing feed streamsbeing treated. Generally the catalyst composition can be used for aperiod of time long enough to accumulate about 20-200 wt. % of metals,mostly Ni and V, based on the initial weight of the catalystcomposition, from the hydrocarbon containing feed. In other words, theweight of the spent catalyst composition will be about 20-200% higherthan the weight of the fresh catalyst composition.

Generally, at least a portion of the hydrotreated product stream havingreduced metal and sulfur contents is subsequently cracked in a crackingreactor, e.g. in a fluidized catalytic cracking unit, under suchconditions as to produce lower boiling hydrocarbon materials suitablefor use as gasoline, diesel fuel, lubricating oils and other usefulproducts. It is within the scope of this invention to hydrotreat saidproduct stream having reduced metal and sulfur contents in one or moreprocesses using different catalyst compositions, such as commercialalumina-supported NiO/MoO₃ catalysts, for further removal of sulfur andother impurities, before the product stream is introduced into thecracking reactor.

A further embodiment of this invention is a hydrofining processcomprising the step of introducing at least one decomposable metalcompound into the hydrocarbon containing feed stream prior to its beingcontacted with the Ni/V/Al₂ O₃ -containing catalyst composition of thisinvention. The metal in the decomposable metal compound is selected fromthe group consisting of the metals of Group IV-B, Group V-B, Group VI-B,Group VII-B, Group VIII and IB of the Periodic Table (as defined in"College Chemistry" by Nebergall et al; D. C. Heath and Company, 1972).Preferred metals are molybdenum, tungsten, manganese, chromium,zirconium and copper. Molybdenum is a particularly preferred metal whichmay be introduced as a carbonyl, acetate, acetylacetonate, carboxylate(e.g., octoate), naphthenate, mercaptides, dithiophosphate ordithiocarbamate. Molybdenum hexacarbonyl, molybdenum dithiophosphate andmolybdenum dithiocarbamate are particularly preferred additives. Thelife of the catalyst composition and the efficiency of thedemetallization process is improved by introducing at least one of theabove-cited decomposable metal compounds into the hydrocarbon containingfeed, which also contains metals such as nickel and vanadium. Theseadditives can be added continuously or intermittently and are preferablyadded at a time when the catalyst composition of this invention has beenpartially deactivated so as to extend its life.

Any suitable concentration of the additive may be added to thehydrocarbon containing feed stream. In general, a sufficient quantity ofthe additive will be added to the hydrocarbon containing feed stream toresult in a concentration of the metal (preferably molybdenum) of saiddecomposable compounds ranging from about 1 to about 1000 parts permillion by weight and more preferably in the range of about 5 to about100 parts per million in said feed stream.

The following examples are presented in further illustration of theinvention and are not to be considered as unduly limiting the scope ofthis invention.

EXAMPLE I

This example illustrates the preparation of several supported, nickeland vanadium containing hydrofining catalyst compositions.

Catalyst A (Invention):

11.7 grams of NH₄ VO₃ and 11.8 grams of NiCO₃ were mixed with 80 mL of aconcentrated aqueous ammonia solution in a 250 mL Erlenmeyer flask. Themixture was stirred for 15 minutes and was slowly (over a period of 15minutes) diluted with distilled water to a total volume of ˜150 mL. Thetotal weight of the contents of the flask was about 166 grams. Most ofthe solution was decanted; the rest was filtered. A small amount (about0.1 gram) of an insoluble solid was discarded. The solution containedabout 0.1 mole of vanadium and 0.1 mole of nickel.

2 mL of concentrated aqueous ammonia was diluted with 15 mL of distilledwater. Then 3.71 grams of the above-described Ni/V-containing solutionwas added to the dilute ammonia solution. This mixture was diluted withdistilled water to a total volume of 24 mL and then mixed with 26.0grams of alumina (provided by American Cyanamid Company, Wayne, NJ underthe designation SN 5982; BET/N₂ surface area: 171 m² /g; mercury porevolume: 0.94 cc/g). The total mixture was air-dried at room temperaturefor about 1 hour and then dried/calcined in a furnace as follows: 100°F.→400° F. within 30 minutes; 2 hours at 400° F.; 400° F.→500° F. within30 minutes; 1 hour at 500° F.; 500° F.→800° F. within 30 minutes; 3hours at 800° F.; 800° F.→room temperature within about 2 hours. Thecalcined catalyst Composition A contained 0.43 weight-% V and 0.50weight-% Ni.

Catalyst B (Control):

This catalyst was prepared by sequential impregnation of alumina withvanadium and nickel. 0.26 gram of NH₄ VO₃ was dissolved in 24 mL ofdilute aqueous ammonia. This solution was mixed with 26.0 of SN 5982alumina, and the wet mixture was air-dried in open dish at roomtemperature for about one hour and then dried/calcined in accordancewith the procedure described for Catalyst A. Thereafter, 0.65 gram ofNi(NO₃)₂ ·6H₂ O was dissolved in enough water to make 24 mL of anaqueous solution, which was mixed with the calcined vanadium-impregnatedalumina. The above-described drying/calcining was repeated for theNi/V-impregnated alumina. The calcined Catalyst B contained 0.43weight-% V and 0.50 weight-% Ni.

Catalyst C (Control):

This catalyst was prepared by simultaneous impregnation of alumina withan aqueous Ni--V solution, in the absence of ammonia and carbonate ions.1.20 grams of Ni(NO₃)₂ ·6H₂ O and 0.82 gram of VOSO₄ ·2H₂ O weredissolved in enough distilled water to make a solution of 22 mL, whichwas then thoroughly mixed with 24.0 g of SN 5982 alumina. The thusimpregnated alumina was air-dried in an open dish at room temperaturefor several hours, and was then dried/calcined in accordance with theprocedure described for Catalyst A. The calcined Catalyst C contained0.85 weight-% V and 0.98 weight-% Ni (thus twice as much V and Ni asCatalyst A).

EXAMPLE II

In this example, the automated experimental setup for investigating thehydrofining of heavy oils in accordance with the present invention isdescribed. Oil was pumped downward through an induction tube into atrickle bed reactor, 28.5 inches long and 0.75 inches in diameter. Theoil pump used was a reciprocating pump with a diaphragm-sealed head. Theoil induction tube extended into a catalyst bed (located about 3.5inches below the reactor top) comprising a top layer of about 40 cc oflow surface area α-alumina (14 grit Alundum; surface area less than 1 m²/gram), a middle layer of a mixture of 50 cc of hydrofining catalyst A,B, or C and 70 cc of 36 grit Alundum, and a bottom layer of about 30 ccof α-alumina.

The oil feed was a Maya 400F+ residuum containing about 4.0 weight-%sulfur, about 62 ppmw (parts per million by weight) nickel, about 302ppmw vanadium, about 12.7 weight-% Ramsbottom carbon residue, about 0.44weight-% nitrogen, and having an API⁶⁰ gravity of 14.1.

Hydrogen was introduced into the reactor through a tube thatconcentrically surrounded the oil induction tube but extended only tothe reactor top. The reactor was heated with a 3-zone furnace. Thereactor temperature was measured in the catalyst bed at three differentlocations by three separate thermocouples embedded in an axialthermocouple well. The liquid product oil was generally collected everyday for analysis. Excess hydrogen gas vented. The concentrations ofvanadium and nickel in the oil were determined by plasma emissionanalysis; sulfur content was measured by X-ray fluorescencespectrometry; Ramsbottom carbon residue was determined in accordancewith ASTM D524; and N content was measured in accordance with ASTMD3228.

EXAMPLE III

This example illustrates the removal of metals and sulfur from a heavyfeed (Maya 400F+) by hydrotreatment in the presence of Catalysts A, Band C. Pertinent process conditions and test results are summarized inTable I. Only truly comparable run samples obtained at LHSV (cc feed perhour per cc catalyst) values ranging from 0.9 to 1.1 and after at least2 days on stream are listed.

                                      TABLE I                                     __________________________________________________________________________               Hours   Flow %-Removal                                                                             Wt-% Metal                                               on  Temp.                                                                             Rate    of   Loading                                       Run   Catalyst                                                                           Stream                                                                            (°F.)                                                                      (LHSV)                                                                             of S                                                                             (Ni + V)                                                                           on Catalyst                                   __________________________________________________________________________    1     A    107 750 1.02 23.1                                                                             60.3 4.9                                           (Invention)                                                                              136 750 1.00 17.4                                                                             64.8 6.3                                                      160 750 0.94 26.3                                                                             66.6 7.5                                                      210 750 1.03 34.0                                                                             66.3 10.0                                                     274 750 0.98 37.2                                                                             69.1 13.2                                                     301 750 0.98 37.7                                                                             71.2 14.7                                                     328 750 0.98 35.7                                                                             70.9 16.1                                                     356 750 0.92 40.5                                                                             73.4 17.5                                                     384 750 1.04 42.7                                                                             70.6 19.1                                          2     B     88 750 0.96 25.2                                                                             57.1 3.4                                           (Control)  113 750 0.99 21.1                                                                             58.2 4.5                                                      138 750 0.99 27.5                                                                             61.7 5.7                                                      163 750 0.93 33.8                                                                             64.0 6.8                                                      240 750 0.98 35.0                                                                             68.7 10.6                                                     294 750 1.04 35.52                                                                            67.4 13.3                                                     322 750 1.00 39.2                                                                             68.8 14.8                                                     350 750 0.99 43.9                                                                             70.0 16.3                                                     377 750 0.95 40.4                                                                             70.0 17.6                                          3     C     48 750 1.00 --.sup.1                                                                         55.1 1.8                                           (Control)   72 750 0.93 --.sup.1                                                                         57.7 2.7                                                       96 750 1.10 --.sup.1                                                                         55.7 3.7                                                      120 750 0.99 --.sup.1                                                                         62.1 4.8                                                      192 750 1.08 21.8                                                                             65.9 9.3                                                      216 750 1.05 22.4                                                                             65.5 10.5                                                     240 750 0.98 22.7                                                                             68.0 11.6                                                     288 750 1.02 34.2                                                                             70.4 14.6                                          __________________________________________________________________________     .sup.1 Measured data were erroneous.                                     

Data in Table I show that at run times up to about 10 days (240 hours)the removal of nickel and vanadium was higher for invention run 1 usingCatalyst A (prepared by the one-step impregnation process of thisinvention) than for control run 2 (using Catalyst B prepared by atwo-step impregnation process) and for control run 3 (using Catalyst Cprepared by a different one-step impregnation process and containingtwice as much V and Ni than invention Catalyst A). After a period ofabout 10 days, initial differences in catalyst activity were apparentlyobscured by the increases in demetallization activity due to thedeposition of nickel and vanadium compounds contained in the oil ontothe catalysts.

EXAMPLE IV

This example illustrates the effect of the addition of small amounts ofa decomposable molybdenum compound, Mo(CO)₆, to an undiluted Monagaspipeline oil feed containing about 336 ppm V and about 87 ppm Ni on theremoval of these metals in the presence of a commercial hydrofiningcatalyst containing about 0.9 weight-% CoO, 0.5 weight-% NiO, 7.3weight-% MoO and about 91 weight Al₂ O₃, having a surface area of about180 m² /g). LHSV of the feed for both runs ranged from about 1.0 to 1.1cc/cc catalyst/hr, the temperature was about 765° C. (407° C.), thepressure was about 2250 psig, and the hydrogen feed rate was about 4800SCF/barrel oil. Experimental data are summarized in Table II.

                  TABLE II                                                        ______________________________________                                        Days                                                                          on     PPM Mo   %-Removal   PPM Mo %-Removal                                  Stream in Feed  of (Ni + V) in Feed                                                                              % (Ni + V)                                 ______________________________________                                         5     0        64          17     72                                         12-13  0        62          17     71                                         17     0        59          7      70                                         20-21  0        61          7      65                                         26     0        58          7      64                                         32-33  0        53          7      65                                         41     0        52          7      70                                         52-53  0        41          7      66                                         58-59  0        43          4      65                                         ______________________________________                                    

Data in Table II clearly show the beneficial effect of added smallamounts of Mo (as Mo(CO)₆) to the feed on the demetallization of the oilwhen a commercial hydrofining catalyst was used. Based on these results,it is presently preferred to introduce a decomposable compound such asMo(CO)₆ into the feed that is hydrotreated with the catalyst compositionof this invention.

Reasonable variations and modifications are possible within the scope ofthe disclosure and the appended claims.

We claim:
 1. A process for preparing a composition of matter comprisingthe steps of:(A) mixing (a) at least one vanadium and oxygen containingcompound, (b) at least one nickel (II) compound, (c) ammonia, and (d)water, in such amounts and under such conditions as to obtain asolution; (B) mixing the solution obtained in step (A) with analumina-containing support material; (C) heating the mixture obtained instep (B) at a first temperature under such conditions as to at leastpartially dry said mixture; and (D) heating the at least partially driedmixture obtained in step (C) at a second temperature, which is higherthan said first temperature, under such conditions as to activate saidmixture.
 2. A process in accordance with claim 1, wherein said vanadiumand oxygen containing compound (a) is selected from the group consistingof ammonium and alkali metal orthovanadates, ammonium and alkali metalpyrovanadates, ammonium and alkali metal metavanadates, divanadiumpentoxide and hydrated forms thereof, vanadium dioxide and hydratedforms thereof, divanadium trioxide and hydrated forms thereof; and saidnickel (II) compound (b) is selected from the group consisting of nickelcarbonate, nickel bicarbonate, basic nickel carbonate, nickel nitrate,nickel sulfate, nickel halides, nickel acetate, nickel formate, nickeloxalate, nickel carboxylates containing from 3-12 carbon atoms, nickeloxide and nickel hydroxide.
 3. A process in accordance with claim 1,wherein said solution obtained in step (A) comprises about 0.005-4.0mole/l V, about 0.005-4.0 mole/l Ni and about 0.03-10 mole/l NH₃.
 4. Aprocess in accordance with claim 1, wherein said vanadium and oxygencontaining compound is NH₄ VO₃, and said nickel (II) compound is NiCO₃.5. A process in accordance with claim 4, wherein said solution obtainedin step (A) comprises about 0.01-1.5 mole/l V, 0.01-1.5 mole/l Ni and0.1-6 mole/l NH₃.
 6. A process in accordance with claim 1, wherein saidheating conditions in step (C) comprise a temperature ranging from about25° C. to about 200° C. and said heating in step (D) is carried out at atemperature ranging from about 200° C. to about 600° C.
 7. A process inaccordance with claim 1, wherein said alumina-containing support has asurface area ranging from about 20 m² /g to about 350 m² /g.
 8. Acomposition of matter, suitable as a catalyst composition, having beenprepared by a process comprising the steps of:(A) mixing (a) at leastone vanadium and oxygen containing compound, (b) at least one nickel(II) compound, (c) ammonia and (d) water, in such amounts and under suchconditions as to obtain a solution; (B) mixing said solution obtained instep (A) with an alumina-containing support material; (C) heating themixture obtained in step (B) at a first temperature under suchconditions as to at least partially dry said mixture; and (D) heatingthe at least partially dried mixture obtained in step (C) at a secondtemperature, which is higher than said first temperature, under suchconditions as to activate said mixture.
 9. A composition of matter inaccordance with claim 8, wherein said vanadium and oxygen containingcompound (a) is selected from the group consisting of ammonium andalkali metal orthovanadates, ammonium and alkali metal pyrovanadates,ammonium and alkali metal metavanadates, divanadium pentoxide andhydrated forms thereof, vanadium dioxide and hydrated forms thereof,divanadium trioxide and hydrated forms thereof; and said nickel (II)compound is selected from the group consisting of nickel carbonate,nickel bicarbonate, basic nickel carbonate, nickel nitrate, nickelsulfate, nickel halides, nickel acetate, nickel formate, nickel oxalate,nickel carboxylates containing from 3-12 carbon atoms, nickel oxide andnickel hydroxide.
 10. A composition of matter in accordance with claim8, said solution obtained in step (A) comprises about 0.005-4.0 mole/lV, about 0.005-4.0 mole/l Ni, and about 0.03-10 mole/l NH₃.
 11. Acomposition of matter in accordance with claim 9, wherein said vanadiumand oxygen containing compound in NH₄ VO₃, and said nickel (II) compoundis NiCO₃.
 12. A composition of matter in accordance with claim 8,wherein said heating conditions in step (C) comprise a temperatureranging from about 25° C. to about 200° C. and said heating in step (D)is carried out at a temperature ranging from about 200° C. to about 600°C.
 13. A composition of matter in accordance with claim 8 comprisingfrom about 0.1 to about 5.0 weight-% V, based on the weight of theentire catalyst composition; from about 0.1 to about 5.0 weight-% Ni,based on the weight of the entire catalyst composition; and having asurface area ranging from about 20 m² /g to about 350 m² /g.
 14. Acomposition of matter in accordance with claim 8 comprising from about0.5 to about 2.0 weight-% V, based on the entire catalyst composition;from about 0.5 to about 2.0 weight-% Ni, based on the entire catalystcomposition; and having a surface area ranging from about 100 m² /g toabout 250 m² /g.